Cyclisierungsreaktionen lithiierter Fluorsilanole und Aminofluorsiloxane - Kreuzdimerisierung eines Silicenium-Ylids / Cyclisation Reactions of Lithiated Fluorosilanols and Aminofluorosiloxanes - Cross-dimerisation of a Silicenium-Ylid

KOH reacts with bis(isopropyl-trimethylsilyl)-amino-difluorosilane to give the fluoro-silanol 1. An aminofluorosiloxane 2 is obtained in the reaction of [(Me3Si)2N]2SiF2 with KOH via a 1,3-silyl-group migration. The four-membered SiOSiN ring 5 can be prepared in several steps from 1. Six-membered SiO rings 8-10 are formed in the reaction of 1,3-fluorosilanols 6 and 7 with butyllithium. Lithiated 2 reacts with PCl3 to give a four-membered P2N2 ring 11, and with 2-methyl-2-propenal to give two isomeric (2 + 4) cycloadducts 12 and 13. The silicenium ylid formed initially by thermal elimation of LiF from lithiated 2 in PE/THF cross-dimerises to give a Si2N2 ring 14. If the reaction is carried out in n-heptane, the product after recrystallisation from acetone, 16, is an isomer of 14. The crystal structures of 14 and 16 have been determined.